Monoazo dyes of the benzisothiazole series which are not soluble in water

ABSTRACT

Monoazo dyes having a diazo component derived from a 4-amino-7nitro-1,2-benzisothiazole optionally substituted in the 5position by chlorine, bromine, nitro or cyano and a substituted aniline as coupling component. The dyes are eminently suitable for dyeing synthetic linear polyesters.

United States Patent m1 Hagen et al.

MONOAZO DYES OF THE BENZISOTHIAZOLE SERIES WHICH ARE NOT SOLUBLE IN WATER lnventorsi Helmut Hagen, Frankenthal;

Guenter Hansen, Ludwigshafen. both of Germany Assignee: Badische Anilin- & Soda-Fabrik Aktiengcsellschaft, Ludwigshafen (Rhine), German Filed: Sept. 23. 1970 Appl. No.: 74,915

Foreign Application Priority Data Sept. 27. 1969 German 1948996 June 3,1970 German 2027201 US. Cl 260/158; 260/304 lnt. CIF. C09B 29/08: C09B 29/26; DO6P 3/54 Nov. 11,1975

Priman E.\uminer--F|oyd D. Higel AIIUIIIC), Agent. or Firm |ohnston, Keil. Thompson & Shurtleff {57] ABSTRACT Monoazo dyes having a diuzo component derived from a 4-amino-7-nitro-l.Z-benzisothiazole optionall) substituted in the 5-position by chlorine. bromine. nitro or cyano and a substituted aniline as coupling component The dyes are eminently suitable for dye ing synthetic linear polyesters.

3 Claims, N0 Drawings 1 MONOAZO DYES OF THE BENZISOTHIAZOLE SERIES WHICH ARE NOT SOLUBLE IN WATER The invention relates to new and valuable monoazo dyes having the general formula (I):

in which R denotes hydrogen, chlorine, bromine, cyano or nitro; R denotes hydrogen or unsubstituted or substituted alkyl or aralkyl; R denotes unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl; R denotes hydrogen, methoxy or ethoxy; and R denotes hydrogen, chlorine, methyl, acetylamino, chloroacetylamino, hydroxyacetylamino r propionylamino.

Radicals R include for example (besides hydrogen) methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl', B- hydroxyethyl, B-cyanoethyl, B-acetoxyethyl, B-carbomethoxy, B-carboethoxy, B-methoxyethyl, B-ethoxyethyl, B-chloroethyl, l3-(fi-cyanoethoxy)-ethyl, B- acetylethyl, B-phenoxyacetoxyethyl, methylsulfonyloxyethyl, B-(B'-acetylacetoxy)-ethyl, B-hydroxypropyl, 'yhydroxypropyl, B, 'y-dihydroxypropyl, 7-acetylaminopropyl, benzyl and phenylethyl.

R may denote any of the radicals specified for R and also cyclohexyl, phenyl, ethoxyphenyl and methoxyphenyl.

Dyes having the general formula (la):

in which X denotes hydrogen, chlorine, bromine or cyano; R denotes alkyl having one to four carbon atoms or B-hydroxyethyl, ,B-cyanoethyl, B-acetoxyethyl, B-methoxyethyl, fi-carbomethoxyethyl, B-carboethoxyethyl, B-(B'-acetylacetoxy)-ethyl, 84,6 acetylacetoxy)-propyl, B,y-dihydroxypropyl, benzyl or phenylethyl; R denotes alk yl having one to four carbon atoms or B-hydroxyethyl, B-cyanoethyl, ,B-acetoxyethyl, cyclohexyl or phenoxyethyl; R denotes hydrogen. chlorine, methyl or acetylamino; and R had the meanings given above, are of particular industrial importance.

The new dyes are suitable for dyeing synthetic linear polyesters such as polyethylene glycol terephthalate, or compounds having a similar constitution. They have high tinctorial strength and give Bordeaux red to blue dyeings having excellent fastness properties. The carrier method and the high temperature method are suitable dyeing methods.

For the production of dyes having the formula (I), diazo compounds of amines having the general formula are reacted with coupling components having the general formula (III):

N-R1 (III) in which R denotes hydrogen, chlorine, bromine or nitro and R" R- R and R have the meanings given above.

For the production of dyes having the formula (I) in which R denotes cyano, diazo compounds having the general formula (II):

in which R denotes chlorine or bromine are reacted with coupling components having the general formula (III):

N-R1 (III) NHcocH,

The diazotization of the compounds having the formula (ll) and coupling with the compounds having the formula (III) may be carried out by generally known methods. The coupling may take place in aqueous medium with or without solvents such as alcohols (methanol or ethanol), glycols (diethylene glycol) or amides (dimethylformamide or N-methylpyrrolidone).

Exchange of the substituents R (C1 or Br) for the 60 Q cnnococna c,H.ococH OCH 3 c,H,oH

monobutyl ether; pyridine bases such as pyridine, picoline or quinoline; and also acetonitrile, dimethylaniline, dimethylformamide, N-methylpyrrolidone, butyrolactone and dimethylsulfoxide. Pyridine and dimethylsulfoxide and mixtures of these solvents with one another or with other solvents are particularly suitable.

Convenient reaction temperatures are in the range from 40 to 150C, preferably from 80 to 120C.

The duration of the reaction depends on the constitution of the dye; as a rule it amounts to a few hours. The course of the reaction may be followed for example by thin-layer chromatography.

To isolate the dyes having the formula (I) with R denoting CN, the copper salt present in the reaction mix ture may be complexed, e.g. by an alkali metal cyanide. The dye is then suction filtered. The dye may also be dissolved in a solvent (for example acetone) in which 7 8 the copper salt is not soluble and thus freed from the cominued pp Salt- Ex- Shade of dyeing on The invention is illustrated by the following Examample Coupling component Polyester ples. The parts and percentages in the Examples are by weight. 8 (2H 5 violet EXAMPLE 1 23 Parts of 4-amino-7-nitro-1,Z-benzoisothiazole is CQHJCOQCHK dispersed in 200 parts of water and 19 parts of bromine is added while stirring. The mixture is stirred first for 9 C violet one hour at room temperature and then for another two hours at 50C. After cooling, the product is diluted with 500 parts of water and the precipitate is suction C2 i filtered, washed with water and dried in vacuo. 27 parts I of 4-amino-5-bromo-7-nitro-l ,2-benzoisothiazole having a melting point of 324C is obtained. The yield is @-N equivalent to 85% of the theory.

. c,ll.co,Cll 13.7 Parts of 4-amino-5-bromo-7-mtro-1,2-benzolsothiazole is dissolved at 10 to 15C in 100 parts of 96% sulfuric acid. 30 parts of a mixture (17:3) of glacial 20 H acetic acid and propionic acid is then gradually added QM at 0 to 5C to the solution and diazotization is carried C H OCH out at 0 to 5C by dripping in 16.5 parts of nitrosylsul- 2 furic acid (1 1.5% of N 0 The whole is stirred for 3 hours at 0 to 5C and the diazo solution is allowed to 12 1 e flow into a solution of 8.7 parts of N-B-cyanoethyl-N- ethylaniline, 25 parts of water, 10 parts of 36% hydrochloric acid, 1 part of sulfamic acid, 500 parts of ice CSH-NHCOCH= and 500 parts of water. After stirring overnight, the deposited crystalline dye is suction filtered, washed with water until neutral and dried at 50C at subatmospheric pressure. blue black powder is obtained which in 3 CIHOCH: violet finely divlded form dyes polyethylene glycol terephthalate intense violet shades having very good fastness properties. c,ll,o cll,

When the coupling components given in the follow g ing Table are used instead of the coupling component in Example 1, dyes having similar fastness properties are obtained: 14 C,H.0H navy blue N Ex- Shade of dyeing on ample Coupling component polyester C,H,CO,CH, No.

2 C,H.OH navy blue 15 C,H,OH navy blue C2; C2H40CH8 3 C,H.OH violet N\ so 16 /C,H, violet c,l-l,cN 4 c,ll.oll blue CJMFECHB c H OH Cl l7 c,ll.cN red violet 5 C,H.OH violet Q c,H.o cll cl C,H,OH

6 C,l-l,oll blue Q- l8 c,ll,oll navy blue c,ll,oll Q NHCOCH, 5 C H 0H 7 C,H OH greenish blue [9 CH3 navy Hue czl cn NHCOCH; CH

-continued E1 Shade of dyeing on iaqmple Coupling component polyester (X H 3 20 C H OH blue green C,H OH NHCOCH 2] C,H,OH violet C,H,O-CCH 22 C H, navy blue C H OCH 23 C. ,H navy blue c H 3 C,H,OH

24 CJLCN violet C H 3 C2H-IOCHI 25 C,H CN violet c H 3 C,H,OH

26 C ,H:, violet C,H,Cl

EXAMPLE 27 low solid is suction filtered, washed with 100 parts of 55 methanol and dried. 47 parts of 4-amino-7 -nitro-l,2- benzoisothiazole having a melting point of 325C is obtained. This is a yield of 96% of the theory.

9.75 Parts of 4-amino-7-nitro-l,Z-benzoisothiazole is dissolved in 70 parts of 36% hydrochloric acid while stirring for 30 minutes, then I00 parts of ice is added and whild cooling externally 15 parts of a 23% sodium nitrite solution is dripped in. The whole is stirred for 1 hour at 0 to C, a slight excess of nitrite is removed with sulfarnic acid and the diam solution is filtered into a solution of l 1.85 parts of N-B-carbomethoxyethyl-N- B-methoxyethylaniline, 25 parts of water, 8 parts of a 36% hydrochloric acid and 100 parts of ice. The coupling mixture then has 250 parts of a 20% sodium acetate solution added to it and the whole is stirred for another 2 hours. The deposited crystalline dye is suction filtered, washed with water until neutral and dried at 50C at subatmospheric pressure. A deep colored blue black powder is obtained which in finely divided form dyes polyethylene glycol terephthalate in very fast red violet shades.

Similar dyes are obtained with the coupling components specified in the following Table:

Example Coupling component Shade of dyeing on No. polyester 28 C,H.CN Bordeaux C H OCH,

29 C H violet CH 3 CQHQNHCOCH:

30 I N C,l-l OCH; currant CJLOCOCH;

3 I Q C,l-l.OH currant C,H,CO,CH;,

32 C H.OH currant C,H,OCH;,

33 C,H' ,CN Bordeaux 34 C,H,, Currant Cm CH 35 C,H}, currant C,H OCH,

36 C.H violet C H,OH 37 C,H CN red violet 3 C H OCH 38 C H CN Currant 3 C,H,OH

39 C,H=, red violet C,H Cl

40 CH;, currant CJ'LCOQH,

OCH I 4| C;H OH blue C H OH uncocn,

42 C,H,OH red violet C H.OCCH,

1 1 EXAMPLE 43 146 Parts of 4-amino-7-nitro-l ,Z-benzoisothiazole is dissolved at to 10C in 660 parts of concentrated sulfuric acid. At 0 to C, 105 parts of nitrating acid (52% by weight of HNO and 48% by weight of H 80 is added thereto in the course of 2 hours. Then the whole is stirred for another hour, the temperature rising to 20C. The mixture is poured onto 1500 parts of ice and the precipitate is suction filtered, washed with water and dried. 49 parts of 4-amino-5,7-dinitro-l,2- benzoisothiazole is obtained having a melting point of 275 to 277C. The yield is 27% of the theory.

12.0 Parts of 4-amino-5,7-dinitro-l,2-benzoisothiazole is dissolved at to C in 100 parts of 96% sulfuric acid. Then at 0 to 5C, 50 parts of a mixture (17:3) of glacial acetic acid and propionic acid is dripped in and thereafter 16.5 parts of nitrosylsulfuric acid (1 1.5%) at 0 to 5C. The whole is stirred at this temperature for 3 hours and the diazo solution is allowed to flow into a solution of 8.7 parts of N-B-cyanoethyl-N-ethylaniline, 25 parts of water, 7 parts of 36% hydrochloric acid, 1 part of sulfamic acid, 500 parts of ice and 500 parts of water.

After stirring overnight, the crystalline dye is suction filtered, washed with water until neutral and dried at 50C at subatmospheric pressure. It dyes polyester fabric fast blue violet shades.

EXAMPLE 44 195 Parts of 4-amino-7-nitro-l ,2-benzoisothiazole is finely dispersed in 1200 parts of water and then 270 parts of chlorine is passed in during 4 hours at 50C. The whole is stirred for another five hours at room temperature. The precipitate is suction filtered, washed with water and dried in vacuo. 202 parts of 4-amino-5- chloro-7-nitro-l,2-benzoisothiazole is obtained having a melting point of 276 to 278C. This is a yield of 92% of the theory.

1 1.5 Parts of 4-amino-5chloro-7-nitro-1,2-benzoisothiazole is dissolved at 10 to 15C in 100 parts of 96% sulfuric acid, at 0 to 5C 50 parts of a mixture (17:3) of glacial acetic acid and propionic acid is added and diazotization is carried out with 165 parts of nitrosylsulfuric acid (1 1.2% of N 0 at 0 to 5C. The mixture is stirred for another 3 hours at 0 to 5C and then coupled with a solution of 8.7 parts of N-B-cyanoethyl-N- ethylaniline, 25 parts of water, 7 parts of 36% hydrochloric acid, 1 part of sulfamic acid, 1000 parts of ice and 500 parts of water. The whole is allowed to stand overnight and the crystalline dye is then suction filtered, washed until neutral and dried at 50C at subatmospheric pressure. A blue black powder is obtained which in finely divided form dyes polyethylene glycol terephthalate in red violet shades having high fastness to light.

Similar dyes which dye polyesters in the shades indicated are obtained with the same diazo component and the coupling components specified in the following Table.

CH CH CH OH Shade of dyeing on polyester -continued Example Coupling component Shade of dyeing on N04 polyester 60 Q N cm cu Bordeaux cni oficu,

6| C,H OH violet C,H.0H 62 Q C,H violet C,H.OC,l-l

63 N C,H navy blue c H 3 C H JIH -CH,

64 C,H CN red violet c H 3 C,H.OCH,

65 C,H CN currant c H 3 C,H.OH

66 Q C,H, violet C,H,Cl

67 CH, 7 Currant 3 C,H CO,C H,

0C H 3 68 CH, violet H 69 0c 3 c,H.oH blue C H OH NHCOCH, 70 violet Similar dyes are obtained with the diazo component having the formula:

and the following coupling components:

Example Coupling component Shade of dyeing on No. polyester 7l N C,H currant C,H OH

72 CH, red violet C,H OH

73 N CH,- violet c 3 C H ,OH

74 C H, navy blue c 3 CH,IHCH,OH

75 Q C,H OCOCH, Bordeaux C,H O-COCH;,

76 H Bordeaux C,H OH 77 C,H, violet C,H 78 C H violet Q N a "r C ,H OH 79 Q C,H, violet C H,OH

8O @NH-Q red violet 8| N H blue C,H.OH

EXAMPLE 82 l3.7 Parts of 4-amino-5-bromo-7-nitro-l,2-benzoisothiazole is dissolved at 10 to 15C in parts of 96% sulfuric acid. 30 Parts of a mixture (17:3) of glacial acetic acid and propionic acid is then gradually added to the solution at 0 to 5C and diazotization is carried out at 0 to 5C by dripping in l6.5 parts of nitrosylsulfuric acid (11.5% N 0 The whole is stirred for another three hours at 0 to 5C and the diazo solution is allowed to flow into a solution of 8.7 parts of N-B- cyanoethyl-N-ethylaniline, 25 parts of water, 10 parts of 36% hydrochlorid acid, 1 part of sulfamic acid, 500 parts of ice and 500 parts of water. After stirring overnight, the deposited crystalline dye is suction filtered, washed with water until neutral and dried under subatmospheric pressure at 50C.

1 [.48 parts (0.025 mole) of 5-bromo-7-nitro-l ,2- benzoisothiazolyll-azo -p-( N-B-cyanoethyl-N-ethyl aniline is dissolved in 60 parts of dimethylsulfoxide, 4.5 parts of cuprous cyanide is added and the whole is benzoisothiazolyli-azo-p-( N-B-cyanoethyl-N-ethyl aniline is obtained. The dye gives fast navy blue deyings on polyeste r cloth.

After introducing the cyano group, dyes having similar fastness properties are obtained by using the coupling components given in the following Table instead of the coupling components of Example 82.

Example Coupling component Shade of dyeing on No. polyester 83 Q C H OH blue 84 C-,H OH navy blue C H CN 85 C H OH blue C,H OH

86 C H OH blue violet moii 87 4 blue C H OH NHCOCHI 88 OC H, greenish blue c,H.oH

C H,C N

NHCOCH 89 Q C,H, navy blue c,H.co,cH,

90 CH, H-CH navy blue C H CN 9| Q C H.OCH navy blue c,u.co,cH

92 C,H CN navy blue C,H;OCH;

93 C,H, blue c immcocu 94 C,H OC H blue -c0ntinued Example Coupling component Shade of dyeing on No. polyester 95 C,H OH blue C,H CO CH,

96 C,H ,OH blue N G czmocn 97 Q C H navy blue c mc lil-cn CJ-LCN blue violet 9s CQLO-fiCl-l 99 C,H OH blue N Q qmon 100 CH= navy blue 0C H 3 ml C,H OH blue green c,n.ou

NHCOCH;

102 c,H.oH blue C,H 0- CH,

103 C,H, navy blue CJ-L OCH l04 C,H, navy blue C H 0H l05 C, H CN blue violet cmom 106 C,H C N navy blue c,H.0H

107 navy blue -continued Example Coupling component Shade of dyeing on No. polyester 10B C H,0C H blue C,H,OCOCH in) Q N/C2H40H blue c,H.co cH cH,

l 10 C H OC H CN hluc violet l 11 N C H CN violet 1 1'. O C,H navy blue C,H,O(fiCH-,O@

113 Q N C H, 81 blue violet C H,OCCH C--CH H,OSO CH blue violet EXAMPLE 1 l 5 e l 1.5 Parts of 4-amino-5-chloro-7-nitro-1 ,Z-benzoisothiazole is dissolved at to C in 100 parts of 96% sulfuric acid, 50 parts of a mixture (17:3) of glacial acetic acid and propionic acid is added at 0 to 5C and diazotization is carried out with 16.5 parts of nitrosylsulfiric acid I 1.2% of N 0 at 0 to 5C. The mixture is stirred for three hours at 0 to 5C and then coupled with a solution of 7.6 parts of N-B-hydroxyethyl-N- ethylaniline, parts of water, 7 parts of 36% hydrochloric acid, 1 part of sulfamic acid, 1000 parts of ice and 500 parts of water. The whold is stirred overnight and the crystalline dye is suction filtered, washed until neutral and dried at 50C at subatmospheric pressure.

18.9 Parts (0.05 mole) of the 5-chloro-7nitro-1,2- benzoisothiazolyl-4-azo-p-( N-B-hydroxyethyl-N- ethyl)-aniline is dissolved in 100 parts of pyridine, 10.6 parts of cuprous cyanide is added and the whole is stirred for 3 hours at 130C. When the exchange is over (which can be ascertained by thin-layer chromatography) the reaction mixture is cooled, poured onto 1000 parts of water and suction filtered. The residue is digested with acetone and the suspension is filtered. After the acetone has been distilled off, the filtrate is diluted with water, the precipitate is suction filtered and dried at 50C at subatmospheric pressure. 124 Parts of the dye containing cyano groups is obtained which dyes polyester fast navy blue shades.

By using the coupling components given in the following Table instead of the coupling component of Example 34, dyes having similar fastness properties are obtained after the introduction of the nitrile group.

Example Coupling component Shade of dyeing No. on polyester 116 C H, navy blue C H,0H

117 CH: Q navy blue L,H,0H

1 l8 Cli -Q blue 3 C H 0H 1 l9 C H blue CH -lH -CH-,OH CH H 120 C H OCOCH blue violet o H,o cocH..

121 C,H navy blue 12?. navy blue -continued -continued Ex- Example Coupling component Shade of dyeing ample Coupling component Shade of dyeing No. on polyester N on polyester l23 Q N/CH' navy blue i3 N/C2H5 VlOltil blue c,H,oH cm-jn-ocoqm a I24 NH- navy blue I0 I39 /C,H5 navy blue :25 NH- 0cm, blue CI 0C :1 140 c,H, blue 127 ([JLOH navy blue N- (E) NHCO H,

I28 CIHOH blue l4l N C,H,CN navy blue NHCOCH,CI

NHCOCH,

3O C,H.CN navy blue n :3 blue \CH3 NHCOCH,OH NHCocl-i,

130 H bl N--- OCH, e We claim: l. A monoazo dye having the formula:

NHCOCH, y H3 1 0 N- j N=N N 2 2 l3l H- greenish blue N// H4 in which R denotes hydrogen, chlorine, bromine, cyano or nitro; R denotes hydrogen, alkyl having one to four NHCOCH carbon atoms, benzyl; phenylethyl, hydroxyalkyl having two or three carbon atoms, B-methoxyethyl, B- N/ ethoxyethyl, B-butoxyethyl, B-cyanoethyl, carboalkox- \QHDCHI yethyl having a total of four to seven carbon atoms. B- chloroethyl, B-(B'-cyanoethoxy)-ethyl, B-acetylethyl, '33 C H blue mm B-phenoxyacetoxyethyl, B-methylsulfonyloxyethyl, l3- (B'-acetylacetoxy)-ethyl or 'y-acetylaminopropyl; R

J Q I 5S denotes alkyl having one to four carbon atoms, hydroxyalkyl having two to three carbon atoms, B-cyanoethyl, 134 /C,H,CN blue violet alkanoyloxyalkyl having four to six carbon atoms, henyl ethoxyphen l methox hen l or c clohex lcnnococm P Y VP Y Y y R denotes hydrogen, methoxy or ethoxy; and R dens bi I notes hydrogen, chlorine, methyl, methoxy, ethoxy, m acetylamino, propionylamino, chloroacetylamino or c.H.0C0c,H, hydroxyacetylamino.

2. A monoazo dye having the formula: I36 N C,H violet blue IX 3 R5 c,|-r.,0c0cH,ci-n Q 6 I37 violet blue O2N N N N\R OCH,

in which X denotes bromine or eyano; R denotes alkyl CN having one to four carbon atoms; R denotes alkyl hav- C H ing one to four carbon atoms; R denotes hydrogen, 1 N=N N chlorine, methyl or acetylamino; and R denotes hydro- 5 H O H C gen methoxy or ethoxy. C C 5 3. The dye having the formula: I 

1. A MONOAZO DYE HAVING THE FORMULA:
 2. A monoazo dye having the formula:
 3. The dye having the formula: 